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US2702763A - Process for the treatment of fabrics - Google Patents

Process for the treatment of fabrics Download PDF

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US2702763A
US2702763A US274660A US27466052A US2702763A US 2702763 A US2702763 A US 2702763A US 274660 A US274660 A US 274660A US 27466052 A US27466052 A US 27466052A US 2702763 A US2702763 A US 2702763A
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fabric
solution
fabrics
polymer
fading
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US274660A
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James E Pritchard
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Phillips Petroleum Co
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene

Definitions

  • Fabrics serve many irnportant'uses but they also have .
  • the-problems encountered are their lack of resistance to penetration by Water, their failure to resist fading when exposed to gases containing oxides of nitrogen, infiammability, etc.
  • Various attempts have been'rnadeto solvetheseproblems but so far they all'leave something to be desired.
  • An object of this invention is'to provide a new process for the treatrnent of fabrics.
  • a further object ofthis invention is the production of fabrics having desirable properties.
  • Afurther object of this invention is a-process of treatment of fabrics in which the Waterrepellencyiof the fabrics is increased.
  • a furtherobject of this invention is a process of treatment of-fabrics-in which resistance to gas fading of the fabrics is increased.
  • a further object of this invention is to provide-fabricshaving increased water :repellency andresistance to gas fading.
  • the fabric to be treated is impregnated with a polymer of a pyridine derivative containingatleast one vinyl group.
  • This treatment is preferably carried out by impregnating the fabric with an aqueous acid solution of the polymer, and, if desired, subjecting the resulting fabric to an additional treatment with an aqueous solutiomof abasic material so as to convert thepyridinium salt originally formed to the free polymeric base, removing the excess baseby washing with water and finally drying theresultingimpregnated fabric.
  • impregnation -l mean'to include cases where each fiber is treated butnot necessarily where all the interstices of the fabric are filled.
  • fabrics can be treated according to a process of this invention.
  • fabrics such as cotton, linen, wool, silk, and rayon, preferably of close Weave are used.
  • the problem of gasfading is particularly important when dealing with cellulose acetate fabrics, said fabrics being especially subject to vfading when exposed to gases such as are formed by the combustion of fuel gases, illuminating gases, and the like.
  • the oxides of nitrogen, such as N20, NO, N02,.N2O3, and N205 are known to have a deleterious effect on dyed cellulose acetate fabrics, various shades of blue anthraquinone dyes being the most susceptible-to gas fading.
  • the fabric to be treated is immersedin the impregnating solution until it is saturated. Insome instances no further treatment, beyond removing and preferably methyl and ethyl groups.
  • further treatment includes the application of a basic material, such as alkali metal hydrox de, carbonate or bicarbonate, rinsing to removeany excess of basic material, and drying.
  • a basic material such as alkali metal hydrox de, carbonate or bicarbonate
  • This alkaline treating solution which converts the pyridinium salt to the free polymeric base, should be of such concentration that it will not harm the fabric.
  • a concentration not greater than 1 per cent by weight is employed, or, expressed in other terms, a 0.01 N to 0.25 N solution is employed. Only the very dilute solutions should be employed on materials such as wool while stronger concentrations can be employed with more resistant textiles such as cotton.
  • Compounds used for the preparation of the polymers are the monoand divinylpyridines, with the vinyl groups being present in any of the several positions in the pyridine nucleus.
  • Alkyl groups can be presenton the'ring or on the OC-Cal'bOft of the Vinyl group, but the number of carbon atoms in the combined alkyl groups shouldgenerallynot be greater than 12.
  • These alkyl groups are These .compounds have the structural formula where R is selected from the group consisting of hydrogen, alkyl, vinyl, and alpha-methylvinyl groups; at least one and not morethan twoof said groupsbeing vinyl or alpha-methylvinyl; and the total number of carbon atoms in thealkylgroups beingnot greater than 12.
  • Examples of such compounds are Z-vinylpyridine; 2,5-diviny1- pyridine; Z-methyl-S-vinylpyridine; 2,3,4,-trimethyl-5-vinylpyridine; 3,4,5 ,6-tetramethyl-Z-Vinylpyridine; 3-ethy1- 5- vinylpyridine; 2,6-diethyl-4-vinylpyridine; 2-isopropy1-4- nonyl-S-vinylpyridine; 2-methyl-5-undecyl-3-vinylpyridine; 3-dodecyl-4,S-divinylpyridine; 2,4-dimethyl-5,6-dipentyl-3 -vinylpyridine; Z-decyl-S a-methylvinyl) pyridine;
  • the polymeric starting materials employed range from rubbery to solid resinous polymers.
  • copolymers of conjugated diolefins with these pyridine derivatives can beemployed, and in fact it has been found that the copolymer gives agreater amountof water repellency.
  • a copolymer of from 15 to '75 parts by weight of the conjugated diolefin and from to 25 parts by weight of the pyridine derivative containing at least one vinyl group is a 50/ 50 butadiene/Z-methyl- 5-vinylpyridine copolymer, either in the form of the free polymeric baseor the correspondingpyridinium salt.
  • the conjugated diolefin component in the copolymer imparts low water solubility to the product and gives greater flexibility .
  • the pyridine derivative component imparts low oil solubility to the product.
  • .homopolymers of the pyridine derivatives mentioned particularly poly-.Z-vinylpyridine and poly-2- methyl-S-vinylpyridine, can be employed. These homo- .polymers are preferred for improving the resistance to gas fading of the fabrics.
  • good resistance to gas fading is obtalned where copolymers prepared from conjugated diolefins in the range from 0 to 15 parts by Weight and pyridine derivatives containing at least one vinyl from to 85 parts by weight are employed.
  • Conjugated diolefins which containfrom4 to 6 carbon Monomers "parts by weight 100 Water do 180 Soap flakes do 5 S208 do 0.3 Mercaptan blend 1 do 0.4 Temperature C 50 A blend of tertiary C12. C14. and C aliphatic mercaptans 'in aratio of 3 1 z 1 parts by weight.
  • the 75/25 and 50/50 butadiene/Z-methyl-S-vinylpyridine copolymers were short-stopped with 0.1 per cent hydro- 'quinone and stabilized with 2 per cent phenyl-beta-naphthylamine. They were coagulated with acid and brine and washed with base to obtain soap-free polymer containing free pyridine nitrogen.
  • the 2-methyl-5-vinylpyridine homopolymers were precipitated from acidified latex by addition of base. They contained no shortstop or antioxidant and were obtained as soap-free polymers after washin with base and water.
  • Solutions which are employed are prepared by dissolving the polymer in an aqueous solution of an acid.
  • acid solution of the desired concentration generally being prepared first, after which the olymer is added, said polymer going into solution by agitation.
  • a more concentrated solution of acid can be employed than is used in the impregnating solution and the solution diluted to the desired concentration after the polymer is dissolved.
  • a liquid acid such as acetic acid
  • a polymer can be treated with the glacial acid and the mixture then diluted prior to use. Re ardless of the acid concentration employed, the polymer dissolves with the formation of a pvridinium salt. Solvation of the resin can be obtained when only one-fourth of the stoichiometric equivalent of acid is used but lar er amounts of acid.
  • Acids which are a plicab e must possess sufiicient water solubility in order that solutions of the desired concentration can be repared.
  • saturated and unsaturated aliphatic monobasic and dibasic or anic acids can be em- ,ployed as we l as mineral acids.
  • acids which are applicable include formic; acetic. propionic. butvric, oxalic. malrmic. maleic. succinic. glutaric, glvcolic. chloroacetic, dichloroace ic. trichlor acetic. hydrochloric. sulfuric. nitric. and phosphoric.
  • the acidity of the impregnating solution is regulated so that the f brics will .not be harmed during the treating process.
  • the pH is preferabl in the ran e from 2 to 6.
  • the impregnating agent may be employed in therform of a latex.
  • the fabric is immersed in the latex, squeezed to remove excess latex and then oven dried. Following this drying, the soap and other soluble materials are removed by washing after which the material is a ain dried.
  • the amount of treating agent used is dependent upon the type of fabric, the weave, and the ultimate use.
  • amount is generally in the range between 0.04 and 5 pounds of the free polymeric base per 100 pounds of correspondingly increased.
  • the materials of this invention have numerous advancording to Test Method 4245.
  • the water repellency of selected fabrics has been evaluated by two of the test methods described in the 1950 Technical Manual and Year Book of the American Association of Textile Chemists and Colorists.
  • the first method was Tentative Test Method 42-45, Resistance to Penetration of Water by Impact. According to this method, 500 cc. of water from a standard spray head impinges upon the fabric stretched over a piece of blotting paper and held 24 inches below the spray head at an angle of 45 with the water stream.
  • test specimen stretched tightly in a sixinch embroidery hoop
  • the fabric is rated with respect to its water repellency. Ratings are made on a scale of zero to 100 where zero represents complete wetting of upper and lower surfaces and 100 represents complete absence of wetting. A rating of 50 indicates complete wetting of upper fabric surface, 70 signifies partial wetting of upper surface, 80 represents partial wet ting to give a sharp spray-head pattern, and indicates slight random wetting of upper surface.
  • Example I Uniform samples of cotton ticking, rayon, and wool gabardine which had been laundered to remove sizing were impregnated with aqueous actic acid solutions of a 50/50 butadiene/Z-methyl-S-Vinylpyridine copolymer and poly-2-rnethyl-5-vinylpyridine. .
  • the solutions were prepared in the following manner:
  • a 50/50 butadiene/Z-methyl-5-vinylpyridine copolymer was dissolved in a 15 per cent aqueous solution of acetic acid in the proportion of 1.5 grams of copolymer per cc. of solution.
  • Poly-2-methyl-5-vinylpyridine was dissolved in a 15 per cent aqueous solution of acetic acid in the proportion of 1.5 grams polymer per 100 cc. of solution.
  • sample of fabric to be treated was dipped into the impregnating solution, squeezed-to remove excess solution, dried, and some of the samples were then immersed in a 0.05 N sodium hydroxide solu-.
  • Example III Apiece of cotton ticking was immersed in a /25 butadiene/Z-methyl-5-vinyipyridine copolymer latex containing 4 per cent polymer by weight, squeezed dry and 7 0 then dried in an air oven at 60 C. The cloth was then washed to remove soap and other soluble materials and again dried in an air oven at 60 C. For this material the penetration value was 1.0 gram. Following immersion. in carbon tetrachloride for 30 minutes the penetration value was again determined and found to be 2.3 grams.
  • Tests for resistance to gas fading were carried out in an air circulating oven. Test specimens were exposed to an atmosphere containing approximately 3 volume per cent N235 (vapors from an anhydrous HNOs bottle) for a 48-hour period at a temperature of F. The untreated sample changed in color from blue to-purple. Samples impregnated with solutions containing 0;5', 1.0;
  • Example V The procedure of Example IV was employed for preparing solutions containing 0.1, 0.5, 1.0, 2.0, and 8.0 weight per cent poly-2-methyl-5-vinylpyridinium acetate and for using these solutions to impregnate test specimens of blue acetate rayon from which sizing and fading inhibitors had been previously removed.
  • the samples were exposed to a mixture of nitrogen oxides, N203, N02, and NO, produced by the action'of sulfuric acid on sodium nitrite. All the treated samples showed resistance to fading after being heated in the atmosphere containing nitrogen oxides for 16 hours at 140 F. Anuntreated specimen changed to a purple color.
  • Example VI Samples of blue acetate rayon from which sizing and fading inhibitors had been removed were treated in various ways and then exposed for two hours at a temperature of 200 F. to an atmosphere containing vapors from commercial concentrated nitric acid. The method of treating the test specimens and the results obtained are given below. One untreated sample was. reserved as a control.
  • Example VII The procedure of Example TV was employed for preparing solutions containing 1.0, 2.0, and 8.0 wei ht percent poly-2-methyl-S-vinylpyridinium acetate and for using these solutions to impregnate test specimens of li ht blue acetate rayon. One end of each specimen was impregnated with the test solution and each entire specimen was base washed.
  • the acetate ravon employed for making the tests was in the form of ribbon 2% inches wide.
  • a standard of fading was available for comparison.
  • This specimen was a sample of acetate rayon dved to a shade which would correspond to the shade obtained after exposing the untreated test specimens for six months to air containing an average content of nitro en oxides, such as would be present in the air as a result of burning gas.
  • a descri tion of the standard of fading, the ribbon employed for test specimens, and the procedure used for determining resistance to gas fading is found in the 1950 Technical Manual and Year Book of the American Association of Textile Chemists and Colorists, volume XXVI, pp. 88-90.
  • Test specimens which had been impregnated with the poly 2 --methyl 5 vinvlpyridinium acetate solutions described above and also an untreated control sample were exposed t air which had been passed through the flame of a lighted gas burner.
  • a sample of rayon which had been treated with a 2.0 per cent solution of triethanolamine was also included for comparison.
  • Triethanolamine is a known treating agent for acetate rayon to improve resistance to gas fading.
  • a temperature of 60 C. was maintained throughout the test. The samples were allowed to remain in the testing chamber until the control sample showed a change of shade corresponding to that of the standard of fading. This test period is known as one exposure period.
  • Example VIII A sample of poly-2-methyl-5-vinylpyridine was treated with one-fourth the stoichiometric equivalent of glacial acetic acid and water was then added to give a solution containing 7.2 per cent poly-2-methyl-5-vinylpyridine by weight. This soluution was diluted with water to give a stable, opaque dispersion containing 3.6 per cent by weight of poly-Z-methyl-S-vinylpyridine. This dispersion had a pH of 5.1.
  • a sample of light blue cellulose acetate fabric was impregnated with the test solution, squeezed to remove excess solution, dried in an oven at 60 C., and then exposed to air which had been passed through the flame of a lighted gas burner. Slight even fading was observed after two exposure periods. For comparison a sample of cellulose acetate fabric was treated in a similar manner with anraqueous solution containing 3.6 per cent triethanolamine. After two exposure periods reddish spots appeared on this sample.
  • the above methods of treating fabrics can be employed for simultaneously dyeing the fabrics and rendering them resistant to gas fading.
  • the impregnating material is added to the dye bath along with the acetate color, resulting in a single bath operation. It has been found that fabric is impregnated with resin during dyeing if HCO3- is added slowly to the boiling dye bath.
  • Example IX Another method which I have found suitable for applying these polymers to fabrics is to dissolve the impregnating agent in an organic solvent and to apply it to the fabric in this manner. Using this method a piece of cotton ticking was immersed in a 2 per cent carbon tetrachloride solution of a 50/50 butadiene/2-methyl-5- vinylpyridine copolymemr. The fabric was dried at 60 C. in an air oven.
  • This material had a penetration value of 0.1 gram. Following immersion in carbon tetrachloride for 30 minutes the penetration was again determined and found to be 2.3 grams. The untreated material had a penetration of 38 grams.
  • Chlorinated organic compounds can be used as solvents for polymers of these pyridine derivatives and copolymers prepared using the pyridine derivatives in all proportions.
  • Alcohols, ketones, and aldehydes are suitable Where the copolymer is prepared using a major proportion of the pyridine derivative; while hydrocarbons are suitable when the copolymer is prepared using a minor proportion of the pyridine derivative.
  • Example X Fabrics impregnated with the polymeric pyridinium phosphate salts exhibit the desirable property of being flameproof.
  • a solution was prepared by dissolving 1.05 parts by weight of poly-2-vinylpyridine in 18 parts by weight of water containing 0.98 part by weight of orthophosphoric acid (H3PO4) to provide poly- 2-vinylpyridinium dihydrogen phosphate.
  • the mol ratio of pyridine nitrogen to orthophosphoric acid is 1:1.
  • Swatches of cotton cloth were immersed in the solution so formed and were then air dried. Some stiffening was imparted to the cloth. Only half of each swatch was treated leaving the untreated half as a control. Controls were also prepared by immersing swatches of cotton cloth in a 10 weight per cent aqueous solution of sodium phosphate and in a 10 Weight per cent solution of poly-2- vinylpyridinium hydrochloride prepared by combining poly-2-vinyl-pyridine and hydrochloric acid in a mol ratio of 1:1.
  • the polymeric salt is frequently applied in an amount greater than that mentioned previously. This amount is from 1 to 15 pounds per 100 pounds of fabric, preferably 2 to pounds per 100 pounds of fabric based upon the free polymeric base.
  • a method of treating fabrics comprising dissolving in an aqueous solution of an acid a polymer of a pyridine derivative of the formula where R is selected from the group consisting of hydrogen, alkyl, vinyl, and alpha-methyl-vinyl; at least one and not more than two of said groups being selected from the group consisting of vinyl and alpha-methylvinyl; and the total number of carbon atoms in the alkyl groups being not greater than 12; immersing the fabric in said solution; removing and at least partially drying said fabric; immersing said fabric in an aqueous solution of a compound selected from the group consisting of alkali metal hydroxides, carbonates, and bicarbonates to form the free polymer base; washing to remove any excess of the second treating solution; and drying the fabric so treated.
  • the method of claim 7 in which 2-methyl-5-viny1- pyr

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Description

some serious dis advantages.
United States Patent PROCESS FOR THE TREATMENT OF FABRICS James E. Pritchard, Barflesville, 0kla., assignor to Phillips Petroleum Company, a corporation of'Delaware No Drawing. Application Marchfi, 1952, Serial No. 274,660
9' Claims. (Cl. 117-62) pared from pyridine derivatives containing at least one vinyl group.
Fabrics serve many irnportant'uses but they also have .Among some of :the-problems encountered are their lack of resistance to penetration by Water, their failure to resist fading when exposed to gases containing oxides of nitrogen, infiammability, etc. Various attempts have been'rnadeto solvetheseproblems but so far they all'leave something to be desired.
By the various aspects of this inventionone or more of the following objects will beobtained.
An object of this invention is'to provide a new process for the treatrnent of fabrics. A further object ofthis invention is the production of fabrics having desirable properties. Afurther object of this inventionis a-process of treatment of fabrics in which the Waterrepellencyiof the fabrics is increased. A furtherobject of this invention is a process of treatment of-fabrics-in which resistance to gas fading of the fabrics is increased. A further object of this invention is to provide-fabricshaving increased water :repellency andresistance to gas fading. A-further :ob-
ject is to provide fabrics which are non-inflammable. Other objects and advantages .of this invention .Will becomeapparent to one skilled-in the art-upon reading this disclosure.
In accordance with this invention the fabric to be treated is impregnated with a polymer of a pyridine derivative containingatleast one vinyl group. This treatment is preferably carried out by impregnating the fabric with an aqueous acid solution of the polymer, and, if desired, subjecting the resulting fabric to an additional treatment with an aqueous solutiomof abasic material so as to convert thepyridinium salt originally formed to the free polymeric base, removing the excess baseby washing with water and finally drying theresultingimpregnated fabric. By impregnation -l mean'to include cases where each fiber is treated butnot necessarily where all the interstices of the fabric are filled.
Various fabrics can be treated according to a process of this invention. Where water repellency is desired, fabrics, such as cotton, linen, wool, silk, and rayon, preferably of close Weave are used. The problem of gasfading is particularly important when dealing with cellulose acetate fabrics, said fabrics being especially subject to vfading when exposed to gases such as are formed by the combustion of fuel gases, illuminating gases, and the like. The oxides of nitrogen, such as N20, NO, N02,.N2O3, and N205 are known to have a deleterious effect on dyed cellulose acetate fabrics, various shades of blue anthraquinone dyes being the most susceptible-to gas fading.
In this process the fabric to be treated is immersedin the impregnating solution until it is saturated. Insome instances no further treatment, beyond removing and preferably methyl and ethyl groups.
. above,
group in the range drying, is necessary, since the fabric at this stage has the desirable properties. In other cases, further treatment includes the application of a basic material, such as alkali metal hydrox de, carbonate or bicarbonate, rinsing to removeany excess of basic material, and drying.
It is not necessary and usually not desirableto dry the fabric before immersing it in the basic solution. However, it may be desirable to remove some of the Water in order that substantially all the polymeric material, which is in the form of a pyridinium salt, will adhere to the textile during treatment with the basic solution. This alkaline treating solution, which converts the pyridinium salt to the free polymeric base, should be of such concentration that it will not harm the fabric. Preferably, a concentration not greater than 1 per cent by weight is employed, or, expressed in other terms, a 0.01 N to 0.25 N solution is employed. Only the very dilute solutions should be employed on materials such as wool while stronger concentrations can be employed with more resistant textiles such as cotton.
Compounds used for the preparation of the polymers are the monoand divinylpyridines, with the vinyl groups being present in any of the several positions in the pyridine nucleus. Alkyl groups can be presenton the'ring or on the OC-Cal'bOft of the Vinyl group, but the number of carbon atoms in the combined alkyl groups shouldgenerallynot be greater than 12. These alkyl groups are These .compounds have the structural formula where R is selected from the group consisting of hydrogen, alkyl, vinyl, and alpha-methylvinyl groups; at least one and not morethan twoof said groupsbeing vinyl or alpha-methylvinyl; and the total number of carbon atoms in thealkylgroups beingnot greater than 12. Examples of such compounds are Z-vinylpyridine; 2,5-diviny1- pyridine; Z-methyl-S-vinylpyridine; 2,3,4,-trimethyl-5-vinylpyridine; 3,4,5 ,6-tetramethyl-Z-Vinylpyridine; 3-ethy1- 5- vinylpyridine; 2,6-diethyl-4-vinylpyridine; 2-isopropy1-4- nonyl-S-vinylpyridine; 2-methyl-5-undecyl-3-vinylpyridine; 3-dodecyl-4,S-divinylpyridine; 2,4-dimethyl-5,6-dipentyl-3 -vinylpyridine; Z-decyl-S a-methylvinyl) pyridine;
3,5-di(a-methylvinyDpyridine; and the like.
The polymeric starting materials employed range from rubbery to solid resinous polymers. In addition, copolymers of conjugated diolefins with these pyridine derivatives can beemployed, and in fact it has been found that the copolymer gives agreater amountof water repellency.
;For waterrepellency i prefer to use a copolymer of from 15 to '75 parts by weight of the conjugated diolefin and from to 25 parts by weight of the pyridine derivative containing at least one vinyl group. A specific example of a copolymer which imparts excellent water repellency characteristics to a fabric is a 50/ 50 butadiene/Z-methyl- 5-vinylpyridine copolymer, either in the form of the free polymeric baseor the correspondingpyridinium salt.
The conjugated diolefin component in the copolymer imparts low water solubility to the product and gives greater flexibility .While the pyridine derivative component imparts low oil solubility to the product. However, .homopolymers of the pyridine derivatives mentioned particularly poly-.Z-vinylpyridine and poly-2- methyl-S-vinylpyridine, can be employed. These homo- .polymers are preferred for improving the resistance to gas fading of the fabrics. However, good resistance to gas fading is obtalned where copolymers prepared from conjugated diolefins in the range from 0 to 15 parts by Weight and pyridine derivatives containing at least one vinyl from to 85 parts by weight are employed.
Conjugated diolefins which containfrom4 to 6 carbon Monomers "parts by weight 100 Water do 180 Soap flakes do 5 S208 do 0.3 Mercaptan blend 1 do 0.4 Temperature C 50 A blend of tertiary C12. C14. and C aliphatic mercaptans 'in aratio of 3 1 z 1 parts by weight.
The 75/25 and 50/50 butadiene/Z-methyl-S-vinylpyridine copolymers were short-stopped with 0.1 per cent hydro- 'quinone and stabilized with 2 per cent phenyl-beta-naphthylamine. They were coagulated with acid and brine and washed with base to obtain soap-free polymer containing free pyridine nitrogen. The 2-methyl-5-vinylpyridine homopolymers were precipitated from acidified latex by addition of base. They contained no shortstop or antioxidant and were obtained as soap-free polymers after washin with base and water.
Solutions which are employed are prepared by dissolving the polymer in an aqueous solution of an acid. the
' acid solution of the desired concentration generally being prepared first, after which the olymer is added, said polymer going into solution by agitation. Sometimes, a more concentrated solution of acid can be employed than is used in the impregnating solution and the solution diluted to the desired concentration after the polymer is dissolved. ln instances where a liquid acid, such as acetic acid, is used. a polymer can be treated with the glacial acid and the mixture then diluted prior to use. Re ardless of the acid concentration employed, the polymer dissolves with the formation of a pvridinium salt. Solvation of the resin can be obtained when only one-fourth of the stoichiometric equivalent of acid is used but lar er amounts of acid. even u to several chemical eouivalents can be used conveniently. The solution should be sufficiently dilute with respect to the nolvmer that uniform impre nation of the fabric can be facilitated. Solutions of polymer ran in in concentration from 0.1 to by weight are fre uently employed.
, Acids which are a plicab e must possess sufiicient water solubility in order that solutions of the desired concentration can be repared. With saturated and unsaturated aliphatic monobasic and dibasic or anic acids can be em- ,ployed as we l as mineral acids. Examples of acids which are applicable include formic; acetic. propionic. butvric, oxalic. malrmic. maleic. succinic. glutaric, glvcolic. chloroacetic, dichloroace ic. trichlor acetic. hydrochloric. sulfuric. nitric. and phosphoric. The acidity of the impregnating solution is regulated so that the f brics will .not be harmed during the treating process. The pH is preferabl in the ran e from 2 to 6.
In another embodiment of my invention, the impregnating agent may be employed in therform of a latex. In this treatment, the fabric is immersed in the latex, squeezed to remove excess latex and then oven dried. Following this drying, the soap and other soluble materials are removed by washing after which the material is a ain dried.
The amount of treating agent used is dependent upon the type of fabric, the weave, and the ultimate use. The
amount is generally in the range between 0.04 and 5 pounds of the free polymeric base per 100 pounds of correspondingly increased.
The materials of this invention have numerous advancording to Test Method 4245.
tages. They are readily applied tothe fabric in the form of dilute aqueous solutions and require only ordinary drying with no special heat treatment to insure a permanent finish. They are resistant to laundering and dry cleaning. The solutions employed impregnate the fibers instead of forming a coating on the surface of the material and are therefore to be preferred over coatings which have a tendency to flake off or crack and which are therefore less permanent. Furthermore, where the fabric is impregnated rather than coated the natural hand of the fabric is not changed.
In the following tests, the water repellency of selected fabrics has been evaluated by two of the test methods described in the 1950 Technical Manual and Year Book of the American Association of Textile Chemists and Colorists. The first method was Tentative Test Method 42-45, Resistance to Penetration of Water by Impact. According to this method, 500 cc. of water from a standard spray head impinges upon the fabric stretched over a piece of blotting paper and held 24 inches below the spray head at an angle of 45 with the water stream.
Standard Test Method 22-41, Resistance to Water Spray;
In this method the test specimen, stretched tightly in a sixinch embroidery hoop, is held at a 45 degree angle six inches below a standard spray head. After pouring 250 cc. of water through the spray head the fabric is rated with respect to its water repellency. Ratings are made on a scale of zero to 100 where zero represents complete wetting of upper and lower surfaces and 100 represents complete absence of wetting. A rating of 50 indicates complete wetting of upper fabric surface, 70 signifies partial wetting of upper surface, 80 represents partial wet ting to give a sharp spray-head pattern, and indicates slight random wetting of upper surface.
Example I Uniform samples of cotton ticking, rayon, and wool gabardine which had been laundered to remove sizing were impregnated with aqueous actic acid solutions of a 50/50 butadiene/Z-methyl-S-Vinylpyridine copolymer and poly-2-rnethyl-5-vinylpyridine. .The solutions were prepared in the following manner:
1. A 50/50 butadiene/Z-methyl-5-vinylpyridine copolymer was dissolved in a 15 per cent aqueous solution of acetic acid in the proportion of 1.5 grams of copolymer per cc. of solution.
2. A portion of solution No. 1 was diluted with twice its volume of water to give a solution containing 0.5 gram of copolymer per 100 cc.
3. Poly-2-methyl-5-vinylpyridine was dissolved in a 15 per cent aqueous solution of acetic acid in the proportion of 1.5 grams polymer per 100 cc. of solution.
In each case the sample of fabric to be treated was dipped into the impregnating solution, squeezed-to remove excess solution, dried, and some of the samples were then immersed in a 0.05 N sodium hydroxide solu-.
in various ways and then tested for water repellency.
Details of treatment of each sample follow.
a. Water-repellency test as described above, measured by increase in weight of blotting paper.
b. Sample from (a) was dried, immersed in carbon tetrachloride for 10 minutes, removed and carbon tetrachloride evaporated, md the water-repellency test repeated.
0. Sample from '(b) was laundered at 100 F. for 10 minutes in a sodium soap solution containing 5 grams of 88 per cent neutralized stearic acid per liter of water, rinsed, dried, and the water-repellency test made as before.
d. Sample from (c) was treated for 30 minutes with a F. soap solution prepared as in '(c), rinsed, dried, and tested for water repellency.
e. Sample from (d) was dried, immersed in carbon tetrachloride, for one hour, removed and carbon tetra- The following table presents results'of tests madeac- 4 OZ. COTTON TIGKING Impact Penetration, grams Impregnsting Solution No. z i 5 a b c d e 0. 6 0. 6 0. 7 g 0. 4 1. 5 2.1 1. 7 s. 2 3 26 NonetUntreatedsample) 36. 5
8 OZ. RAYON GABARDI'NE Example 11 it) Quagrtrty has of Fabric in solu h Penetra- Test tion Pounds Rum? Fabric 0 26 9 oz. Cotton Twill 1 9 002 4oz; .Cotton'licking; 3 i 58 g so 1002. Cotton Duck 2 no 100 JO 0 19 70 8' oz; Rayon Gabardine 0. 6 0 80 l. 8 O. 1 80 6 02. Wool Flannel g 9 8: Z 0 9. 4 10 oz. Wool Gabardine 0.7 O 90 1. 7 0 90 It is noted that spray test ratings of 80 to 100 were obtained for the treated fabrics. These values indicate that the fabrics and yarns were highly water repellent. Ratings inthis test are dependent upon the characteristics of the fibers and not upon fabric construction. Ratings in the impact penetration test are dependent to a great xtenton'the' type of weave.
Example III Apiece of cotton ticking was immersed in a /25 butadiene/Z-methyl-5-vinyipyridine copolymer latex containing 4 per cent polymer by weight, squeezed dry and 7 0 then dried in an air oven at 60 C. The cloth was then washed to remove soap and other soluble materials and again dried in an air oven at 60 C. For this material the penetration value was 1.0 gram. Following immersion. in carbon tetrachloride for 30 minutes the penetration value was again determined and found to be 2.3 grams.
Similar tests were performed with cotton ticking using a polybutadiene latex diluted to contain approximately 4 per cent polymer by weight. The original treated material had a penetration value of 2.4 grams. Treatment with carbon tetrachloride for 30 minutes produced material-which showed no water repcllency, i. e., the arnount of. water was in excess of that which could be measured accurately on the blotter.
The determination ofthe resistance to gas fading was made in two different ways, treatment with the gas given off from nitric acid, and also a regular test as specified by the American Association of Textile Chemists and Colorists. These two methods are discussed in connecion with the specific example in which they are use Example IV Samples of bright blue acetate rayon were treated to remove sizing, materials for inhibiting. fading, etc.,. by immersing them in carbon tetrachloride for 10 minutes, evaporating the solvent, and then laundering them' at F. for 10 minutes in av sodium. soap solution. con taining 5 grams of 88 per cent. neutralized stearic acid per liter of water. One sample was reserved as a' control and the rest were impregnated with aqueous acetic: acid solutions of poly-Zunethyl-Svinylpyridine of variable concentrations. The polymeric starting material was a white powder. Stoichiometric quantities. of acetic acid and the polymer were employed, that. is, an. amount of acetic acid equivalent to the basic groups in the polymer. After the polymer dissolved in the acid-to-formthe pyridinum salt, difierent portions of this solution were diluted to give solutions conta-iningthe following concentrations of polymer acetate:
(1) 0.1 weight per cent (2) 0.5 weight per cent ('3) 1.0 weight percent (4) 2.0 weight per cent One sample of cloth was immersed in each impregnating' solution, squeezed to. remove: excesssolution, dried, and then immersed in a 0.0.5 N sodium hydroxide solution. The samples were then rinsed to remove excess sodium hydroxide and dried. The cloth after treatment had the same feel or hand as the untreated material.
Tests for resistance to gas fading were carried out in an air circulating oven. Test specimens were exposed to an atmosphere containing approximately 3 volume per cent N235 (vapors from an anhydrous HNOs bottle) for a 48-hour period at a temperature of F. The untreated sample changed in color from blue to-purple. Samples impregnated with solutions containing 0;5', 1.0;
g and 2.0 per cent polymer acetate, respectively, showed a very noticeable improvement (resistance to fading). Some improvement was noted when solution 1, containing 0.1 per cent polymer acetate, was used.
Additional samples of the acetate rayon used in previous tests, and treated to remove sizing, etc., were weighed and immersed in treating solutions 1' to 4' hereinabove described, squeezed to remove excess solution, and weighed. Calculations showed that the polymer was applied at the following rates using the different treating solutions:
(1) 0.04 pound per 100 pounds of fabric (2) 0.20 pound per 100 pounds of fabric (3) 0141 pound per 100 pounds of fabric (4) 0.82 pound per 100 pounds of fabric Example V The procedure of Example IV was employed for preparing solutions containing 0.1, 0.5, 1.0, 2.0, and 8.0 weight per cent poly-2-methyl-5-vinylpyridinium acetate and for using these solutions to impregnate test specimens of blue acetate rayon from which sizing and fading inhibitors had been previously removed. The samples were exposed to a mixture of nitrogen oxides, N203, N02, and NO, produced by the action'of sulfuric acid on sodium nitrite. All the treated samples showed resistance to fading after being heated in the atmosphere containing nitrogen oxides for 16 hours at 140 F. Anuntreated specimen changed to a purple color.
Example VI Samples of blue acetate rayon from which sizing and fading inhibitors had been removed were treated in various ways and then exposed for two hours at a temperature of 200 F. to an atmosphere containing vapors from commercial concentrated nitric acid. The method of treating the test specimens and the results obtained are given below. One untreated sample was. reserved as a control.
(1 Sample treated with an 8 weight per cent aqueous solution of poly-2-methvl-5-vinylpyridinium acetate, dried, and then washed with sodium hydroxide solution, rinsed. and dried. The sample remained substantially unfaded when exposed to an atmosphere containing nitric acid vapors.
(2) Sample prepared as in 1) was laundered for 10 mmutes at 100 F. in a sodium soap solution containing grams of 88 percent neutralized stearic acid per liter of water. The fabric showed good resistance to fading when exposed to an atmosphere containing nitric acid vapors.
(3) Sample prepared as in (1) was dry cleaned by immersing It in carbon tertachloride for minutes. No fading was observed after exposure to nitric acid vapors.
(4) Sample treated with an 8 weight per cent aqueous solution of triethylenetetramine, dried. rinsed. and dried. No resistance to fading was accomplished. The sample had the same appearance as the untreated fabric, the blue color changing to reddish purple.
(5) Sample treated with an 8 weight per cent aqueous solution of triethvlenetetramine and dried. Considerable resistance to fading was observed. (It is known that polyamines of this type have been used to effect resistance to gas fading but the finish is not permanent.) The treating agent is readily washed out upon laundermg as shown in test (4). i
(6) Sample treated with an 8 weight per cent aqueous solution of poly-2-vinylpyridinium acetate, dried. washed with sodium hvdroxide solution. rinsed. and dried. Some resistance to fading was observed after exposure to an atmosphere containing nitric acid vapors.
(7) Sample from which sizing, inhibitors for fading, etc., had been removed, but otherwise untreated, was exposed to an atmosphere containing nitric acid vapors. The blue color changed to reddish purple.
Example VII The procedure of Example TV was employed for preparing solutions containing 1.0, 2.0, and 8.0 wei ht percent poly-2-methyl-S-vinylpyridinium acetate and for using these solutions to impregnate test specimens of li ht blue acetate rayon. One end of each specimen was impregnated with the test solution and each entire specimen was base washed.
The acetate ravon employed for making the tests was in the form of ribbon 2% inches wide. A standard of fading was available for comparison. This specimen was a sample of acetate rayon dved to a shade which would correspond to the shade obtained after exposing the untreated test specimens for six months to air containing an average content of nitro en oxides, such as would be present in the air as a result of burning gas. A descri tion of the standard of fading, the ribbon employed for test specimens, and the procedure used for determining resistance to gas fading is found in the 1950 Technical Manual and Year Book of the American Association of Textile Chemists and Colorists, volume XXVI, pp. 88-90.
Test specimens which had been impregnated with the poly 2 --methyl 5 vinvlpyridinium acetate solutions described above and also an untreated control sample were exposed t air which had been passed through the flame of a lighted gas burner. A sample of rayon which had been treated with a 2.0 per cent solution of triethanolamine was also included for comparison. (Triethanolamine is a known treating agent for acetate rayon to improve resistance to gas fading.) A temperature of 60 C. was maintained throughout the test. The samples were allowed to remain in the testing chamber until the control sample showed a change of shade corresponding to that of the standard of fading. This test period is known as one exposure period. When making these tests, in the event that any of the samples being tested show no fading, they are again suspended in the testing chamber together with a fresh control. When the control specimen shows a change in shade corresponding to that of the standard of fading, a second exposure period is indicated. This procedure is repeated as often as is necessary or desired to disclose the number of exposure periods necessary to produce an appreciable alteration in shade. After each exposure period the samples are removed from the testing chamber and compared with 8. the respective unexposed portions of the specimens. The following method of rating is used:
No. of Rating Exposure Shade Change Periods 1 Appreciable.
1 No appreciable. Very good 2 D Earm llpnt 3.5 D
Using the above method of rating, the following results were obtained with the samples impregnated with the solutions hereinbefore described:
The effect obtained with triethanolamine was good, as noted above, after one exposure period but its inhibiting activity decreased markedly upon further exposure in the testing chamber.
Example VIII A sample of poly-2-methyl-5-vinylpyridine was treated with one-fourth the stoichiometric equivalent of glacial acetic acid and water was then added to give a solution containing 7.2 per cent poly-2-methyl-5-vinylpyridine by weight. This soluution was diluted with water to give a stable, opaque dispersion containing 3.6 per cent by weight of poly-Z-methyl-S-vinylpyridine. This dispersion had a pH of 5.1. A sample of light blue cellulose acetate fabric was impregnated with the test solution, squeezed to remove excess solution, dried in an oven at 60 C., and then exposed to air which had been passed through the flame of a lighted gas burner. Slight even fading was observed after two exposure periods. For comparison a sample of cellulose acetate fabric was treated in a similar manner with anraqueous solution containing 3.6 per cent triethanolamine. After two exposure periods reddish spots appeared on this sample.
The above methods of treating fabrics can be employed for simultaneously dyeing the fabrics and rendering them resistant to gas fading. The impregnating material is added to the dye bath along with the acetate color, resulting in a single bath operation. It has been found that fabric is impregnated with resin during dyeing if HCO3- is added slowly to the boiling dye bath.
Example IX Another method which I have found suitable for applying these polymers to fabrics is to dissolve the impregnating agent in an organic solvent and to apply it to the fabric in this manner. Using this method a piece of cotton ticking was immersed in a 2 per cent carbon tetrachloride solution of a 50/50 butadiene/2-methyl-5- vinylpyridine copolymemr. The fabric was dried at 60 C. in an air oven.
This material had a penetration value of 0.1 gram. Following immersion in carbon tetrachloride for 30 minutes the penetration was again determined and found to be 2.3 grams. The untreated material had a penetration of 38 grams.
Chlorinated organic compounds can be used as solvents for polymers of these pyridine derivatives and copolymers prepared using the pyridine derivatives in all proportions. Alcohols, ketones, and aldehydes are suitable Where the copolymer is prepared using a major proportion of the pyridine derivative; while hydrocarbons are suitable when the copolymer is prepared using a minor proportion of the pyridine derivative.
9 Example X Fabrics impregnated with the polymeric pyridinium phosphate salts exhibit the desirable property of being flameproof. To demonstrate this a solution was prepared by dissolving 1.05 parts by weight of poly-2-vinylpyridine in 18 parts by weight of water containing 0.98 part by weight of orthophosphoric acid (H3PO4) to provide poly- 2-vinylpyridinium dihydrogen phosphate. The mol ratio of pyridine nitrogen to orthophosphoric acid is 1:1.
Swatches of cotton cloth were immersed in the solution so formed and were then air dried. Some stiffening was imparted to the cloth. Only half of each swatch was treated leaving the untreated half as a control. Controls were also prepared by immersing swatches of cotton cloth in a 10 weight per cent aqueous solution of sodium phosphate and in a 10 Weight per cent solution of poly-2- vinylpyridinium hydrochloride prepared by combining poly-2-vinyl-pyridine and hydrochloric acid in a mol ratio of 1:1.
In order to test these materials the untreated end of each specimen was ignited and in each case the flames propagated readily in the untreated cloth. The hydrochloric acid salt of the polymer exhibited no flame retardant properties. Cloth treated with sodium phosphate smoldered for several minutes and continued to char. The cloth treated with the phosphate salt of the polymer did not support any type of combustion.
For the purpose of flameproofing, i. e. not capable of supporting combustion, the polymeric salt is frequently applied in an amount greater than that mentioned previously. This amount is from 1 to 15 pounds per 100 pounds of fabric, preferably 2 to pounds per 100 pounds of fabric based upon the free polymeric base.
As many possible embodiments may be made of this invention without departing from the scope thereof, it is to be understood that all matter herein set forth is to be interpreted as illustrative and not in a limiting sense.
I claim:
1. A method of treating fabrics comprising dissolving in an aqueous solution of an acid a polymer of a pyridine derivative of the formula where R is selected from the group consisting of hydrogen, alkyl, vinyl, and alpha-methyl-vinyl; at least one and not more than two of said groups being selected from the group consisting of vinyl and alpha-methylvinyl; and the total number of carbon atoms in the alkyl groups being not greater than 12; immersing the fabric in said solution; removing and at least partially drying said fabric; immersing said fabric in an aqueous solution of a compound selected from the group consisting of alkali metal hydroxides, carbonates, and bicarbonates to form the free polymer base; washing to remove any excess of the second treating solution; and drying the fabric so treated.
2. The method of claim 1 in which said aqueous solution contains from 0.1 to per cent by weight of the polymer and the basic solution has a normality of from 0.01 N to 0.25 N.
3. A method of treating fabrics, made of fibers selected from the group consisting of cellulose, cellulose acetal, and protein fibers, comprising dissolving in an aqueous solution of an acid a polymer of a pyridine derivative of the formula where R is selected from the group consisting of hydrogen, alkyl, vinyl, and alpha-methylvinyl; at least one and not more than two of said groups being selected from the group consisting of vinyl and alpha-methylvinyl; and the total number of carbon atoms in the alkyl groups being not greater than 12; immersing the fabric in said solution; immersing said fabric in an aqueous solution of a compound selected from the group consisting of alkali metal hydroxides and carbonates to form the free polymer base; washing to remove any excess of the second treating solution; and drying the fabric so treated.
4. The method of claim 3 in which the fabric is made of cotton fibers.
5. The method of claim 3 in which the fabric is made of wool fibers.
6. The method of claim 3 in which the fabric is made of cellulose acetate fibers.
7. A method of treating fabrics comprising preparing an acidic aqueous solution of a polymer prepared by polymerizing a mixture containing a compound selected from the group consisting of conjugated diolefins and compounds containing the CH2=C group, and a pyridine derivative of the formula where R is selected from the group consisting of hydrogen, alkyl, vinyl and alpha-methylvinyl, at least one and not more than two of said groups being of the group consisting of vinyl and alpha-methylvinyl, and the total number of carbon atoms in the alkyl groups being not greater than 12; the weight ratio of the former to the latter being up to 3 to 1; immersing the fabric in said solution; immersing said fabric in an aqueous solution of a compound selected from the group consisting of alkali metal hydroxides, carbonates and bicarbonates to form the free polymer base; washing to remove any excess of the sezond treating solution; and drying the product so treate 8. The method of claim 7 in which 2-methyl-5-viny1- pyridine is the pyridine derivative and butadiene is the polymerizable comonomer.
9. The method of claim 7 in which 2-viny1pyridine is i the pyridine derivative and butadiene is the polymerizable COI'HOHOIIICI'.
References Cited in the file of this patent UNITED STATES PATENTS 2,402,020 Cislak et al. June 11, 1946 2,540,984 Jackson Feb. 6, 1951 2,561,215 Mighton July 17, 1951 2,564,726 Sauer Aug. 21, 1951 FOREIGN PATENTS 369,778 Italy Mar. 29, 1939

Claims (1)

1. A METHOD OF TREATING FABRICS COMPRISING DISSOLVING IN AN AQUEOUS SOLUTION OF AN ACID A POLYMER OF A PYRIDINE DERIVATIVE OF THE FORMULA
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US2828221A (en) * 1955-03-21 1958-03-25 Rohm & Haas Method of coating leather with polymers containing cyclic t-amino groups and the resulting article
US2861902A (en) * 1954-09-07 1958-11-25 Phillips Petroleum Co Addition products of heterocyclic nitrogen polymers and heavy metal salts, method ofimpregnating with, and impregnated article
US2875097A (en) * 1954-09-07 1959-02-24 Phillips Petroleum Co Parasiticides, their preparation and use
US2879824A (en) * 1955-08-10 1959-03-31 Firestone Tire & Rubber Co Coated tubeless tire chafer strip
US2888436A (en) * 1955-02-18 1959-05-26 Phillips Petroleum Co Polyfunctional polymeric products
US2892672A (en) * 1955-02-16 1959-06-30 Celanese Corp Inhibition of gas fading in colored cellulose triacetate
US2992942A (en) * 1957-05-31 1961-07-18 Dow Chemical Co Process for rendering normally flammable cellulosic articles fire retardant
US3021188A (en) * 1958-01-24 1962-02-13 Celanese Corp Textile materials resistant to fading

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Publication number Priority date Publication date Assignee Title
BE565383A (en) * 1957-03-07
FR1388082A (en) * 1963-12-27 1965-02-05 Kuhlmann Ets Process for flame retardant and water repellency of textiles

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Publication number Priority date Publication date Assignee Title
US2402020A (en) * 1942-07-14 1946-06-11 Reilly Tar & Chem Corp Vulcanized synthetic elastomer and process of making it
US2540984A (en) * 1948-10-19 1951-02-06 Monsanto Chemicals Copolymers of vinyl pyridine and polyvinyl aromatic compounds
US2561215A (en) * 1945-06-11 1951-07-17 Du Pont Laminated products and adhesive compositions of matter
US2564726A (en) * 1949-04-19 1951-08-21 Du Pont Polymeric compounds

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2402020A (en) * 1942-07-14 1946-06-11 Reilly Tar & Chem Corp Vulcanized synthetic elastomer and process of making it
US2561215A (en) * 1945-06-11 1951-07-17 Du Pont Laminated products and adhesive compositions of matter
US2540984A (en) * 1948-10-19 1951-02-06 Monsanto Chemicals Copolymers of vinyl pyridine and polyvinyl aromatic compounds
US2564726A (en) * 1949-04-19 1951-08-21 Du Pont Polymeric compounds

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2861902A (en) * 1954-09-07 1958-11-25 Phillips Petroleum Co Addition products of heterocyclic nitrogen polymers and heavy metal salts, method ofimpregnating with, and impregnated article
US2875097A (en) * 1954-09-07 1959-02-24 Phillips Petroleum Co Parasiticides, their preparation and use
US2892672A (en) * 1955-02-16 1959-06-30 Celanese Corp Inhibition of gas fading in colored cellulose triacetate
US2888436A (en) * 1955-02-18 1959-05-26 Phillips Petroleum Co Polyfunctional polymeric products
US2828221A (en) * 1955-03-21 1958-03-25 Rohm & Haas Method of coating leather with polymers containing cyclic t-amino groups and the resulting article
US2879824A (en) * 1955-08-10 1959-03-31 Firestone Tire & Rubber Co Coated tubeless tire chafer strip
US2992942A (en) * 1957-05-31 1961-07-18 Dow Chemical Co Process for rendering normally flammable cellulosic articles fire retardant
US3021188A (en) * 1958-01-24 1962-02-13 Celanese Corp Textile materials resistant to fading

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